JPS61108692A - Hydrotreating and dewaxing method of petroleum charged material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for simultaneously denitrifying, desulfurizing and dewaxing a petroleum charge to produce a lower pour point improved product.

It is well known that many, if not all, petroleum base oils contain contaminants such as sulfur, nitrogen and metals. In particular, it is desirable to remove contaminants when further processing these petroleum base oil charges, an operation that usually requires the use of catalysts.

It is known in the art to remove sulfur from hydrocarbon stocks by treating them with hydrogen in contact with a catalyst containing a hydrogenation component at elevated temperatures and pressures.

Typically, the hydrogenation component of the prior art catalysts mentioned above is from Periodic Table VI
It is a group A metal, a group Ⅰ metal, or an oxide or sulfide thereof. These hydrogenated components include, for example, alumina,
It can be supported on a variety of known supports such as diatomaceous earth, zeolitic molecular sieves and other materials with high surface areas.

In this regard, see U.S. Pat. No. 4,080,296, U.S. Pat. No. 3,546,103.
@ teaches a hydrodesulfurization process using a catalyst comprising cobalt and molybdenum supported on an alumina support.

U.S. Pat. No. 3,755,145 discloses a hydrogenation component,
A process is described for the production of lubricating oils characterized by a low pour point utilizing conventional cracking catalysts which may be crystalline or amorphous and a catalyst mixture consisting of 6 crystalline aluminosilicate mt with a control index of 1 to 12. There is.

U.S. Pat. No. 3,894,938 describes a high pour point, high sulfur content gas oil and a control index of 1 to 1 which can contain hydrogenation/dehydrogenation components in the presence or absence of added hydrogen.
The present invention relates to a process for catalytic dewaxing and desulfurization of said gas oil to a lower sulfur content, comprising contacting a zeolite hydrogenation membrane wax catalyst with a zeolite hydrogenation membrane of 12% and then subjecting the dewaxed intermediate to a conventional hydrodesulfurization treatment.

U.S. Pat. No. 4,458,024 describes a process for hydrotreating and dewaxing petroleum residues with a catalyst containing a zeolite, a hydrogenation component, and alumina with a control index of 1 to 12.

U.S. Pat. No. 4,411,770 describes the hydrogenation of heavy hydrocarbon oils characterized in that the catalyst contains a zeolite or Na-beta component and a metallic hydrogenation component with controlled treatments 1 to 12. The conversion method is described.

U.S. Pat. No. 4,419,220 discloses an isomerization membrane wax process using a catalyst consisting of zeolite beta and a hydrogenation/dehydrogenation component on a support.

Although many improvements have been made, it would be advantageous to have a process that could efficiently and simultaneously hydrotreat and dewax petroleum charges.

Accordingly, the present invention combines a distillable petroleum charge with nitrogen compounds, waxy components and a sulfur content of at least 1.0% by weight and a boiling point above 260° C. with 0.5-30% by weight of zeolite beta. and a support consisting of 99.5 to 70% by weight of an inorganic oxide; and 6 to 25% by weight, based on the total catalyst weight and expressed in elemental form, of at least one selected from iron, cobalt and nickel. contact with a catalyst containing a hydrogenation/dehydrogenation component which is a metal from Group I of the Periodic Table and at least one metal from Group IA of the Periodic Table, converting not more than 15% of said feedstock to light materials; The object of the present invention is to provide a method for simultaneously denitrifying, desulfurizing and dewaxing said feedstock, which comprises producing a liquid product with reduced wax content, nitrogen content and sulfur content.

In the present invention, pores with a diameter of 100λ or less have a catalyst pore volume of 9
zeolite beta; and an inorganic oxide support, preferably alumina. If the catalyst system is manufactured, heavy petroleum fractions such as vacuum distilled gas oil can be hydrotreated and hydrogenated membrane waxed in a single step operation, and the nitrogen and sulfur/gold content can be satisfied, and the pour point can be improved. This is based in part on the finding that it is possible to obtain products that can be substantially reduced. In some cases, the method of the present invention, which does not require further processing, has an economical advantage as it can eliminate previously required subsequent processing steps. Furthermore, if additional treatments are required, the process of the present invention can make subsequent purification operations more efficient. For example, the product produced by the process of the present invention may be further hydrotreated in a second or subsequent step. , conversion or dewaxing is necessary, the initial waxing carried out by the process of the present invention may require dewaxing over a second step catalyst (i.e., NiW or PL on an oxide-free or zeolite support). The method of the present invention can result in various advantages such as the ability to utilize lower temperatures in the second step and an extension of the useful life of the second step catalyst. reduces the number of processing steps and also improves the efficiency of downstream processing steps.

Improve activity and function.

Zeolite Beta is an effective catalyst for hydrofilm waxing a variety of petroleum fractions, including crude heavy petroleum fractions, which effectively lowers the pour point of said fractions. Cobalt-molybdenum or di-/kelumolybdenum supported on alumina is a very effective denitrification/desulfurization catalyst that can effectively reduce the sulfur and nitrogen content of the feedstock, but rarely However, even if it has no effect on the pour point, its effect is extremely small.6 The present inventors have developed a method using hydrogen impregnated on a support consisting of a small proportion of zeolite beta and a major proportion of an inorganic oxide. It has been discovered that a catalyst system comprising the components is capable of simultaneously hydrotreating and dewaxing heavy feedstocks, such as vacuum distilled gas oil (VGO), in a single step operation.

The incorporation of zeolite beta into the support provides the expected dewaxing activity, but does not result in a reduction in hydroprocessing performance.6 The specific properties of the catalyst system utilized in the present invention are as follows. Details are given below.

As mentioned above, the catalyst system of the present invention includes zeolite beta. Zeolite Beta is covered by U.S. Patent No. 3.308,06
No. 9, Mei 4I and U.S. Reissue Patent No. 28,341. Zeolite beta is a crystalline silicate zeolite with a pore size of 5 Å or more.2 The composition of zeolite beta in its as-synthesized form can be expressed as follows: [XNa(1,Ofo,1-X)T
EA]^low 4SiO24HzO In the formula, up to 60 depending on the metal cation abundance (W is the degree of hydration, up to 4 was found to be greater than the originally specified value)
.

TEAIi&min is calculated from the difference between the analytical value of sodium and the theoretical cation/framework aluminum ratio of 1.

In its fully base-exchanged form, zeolite beta has the following composition: [→(1,0th0.1-X)H]Al0z·YS+O
, -WHyO, where χ, Y and W have the values described above, and n is the valence of the metal M. Since it is currently more conventional to write the silica/alumina ratio of the zeolite rather than the silicon/aluminum ratio of the zeolite, the above equation can be written as follows: [→(1,Oto, 1-X)It]AlzOi・YSi
(In the h・1IHaO formula, Y, which determines the silica/alumina ratio, is 10 or more. Therefore, the numerical value of the ratio written as "silica/alumina" is usually 0, which corresponds to twice the silicon/aluminum ratio of the zeolite, e.g. , a silicon/aluminum ratio of 100/L corresponds to a silica/alumina ratio of 200/1. In the following description of this specification, ratios relating to zeolite beta are expressed as silica/alumina ratios.

In its partially base-exchanged form, obtained from the initial sodium form of the zeolite by ion exchange without calcination, zeolite beta has the following composition: [→(1,Oto,1-X)TEA]AhO,' YSi
When O,'WH,0 zeolite beta is used in the present catalyst, the zeolite is at least partially in the hydrogen form, providing the desired acid functionality to carry out the cracking reaction. It is usually preferred to use a form of zeolite with sufficient acid functionality such that the zeolite has an alpha value of 1 or greater. Details of the alpha value, a measure of the acid functionality of zeolites, and methods of measuring it are given in U.S. Pat. No. 4,016,
Specification No. 218 and Z Newk Le Bu Isis J
, Canal sis Volume ■, pp. 278-287 (
(1966). Acid functionality can be adjusted by base exchange of the zeolite with alkali metal cations such as sodium, by steaming, by adjusting the silica/alumina ratio of the zeolite, or by acid extraction of aluminum from the zeolite. I can do it.

When synthesized in the alkali metal form, zeolite beta can be converted to the hydrogen form by ion exchange with ammonium ions to form an ammonium type intermediate and calcination of the ammonium type intermediate to form the hydrogen form. can. In addition to the hydrogen form, other forms of zeolite with initial alkali metal substitution can be used. That is,
The initial alkali metal content of the zeolite can be ion-exchanged with other suitable metal cations including, for example, platinum, nickel, copper, zinc, palladium, calcium or rare earth metals.

Besides having the above-mentioned composition, zeolite beta is further characterized by its X-ray powder diffraction pattern as described in U.S. Patent No. 3,308,069 and U.S. Reissue Patent No. 28,341. I can do it. Zeolite beta can be prepared with very high silica/alumina ratios, for example zeolite beta can be obtained with a silica/alumina ratio of 250/1 or 500/1 or more.

In this specification, the silica/alumina ratio refers to the skeleton structure ratio, that is, the 5ib body and A10. It is the ratio of tetrahedrons. It is to be understood that this ratio may differ from the silica/alumina ratio determined by various physical and chemical methods. may be included, thereby resulting in a low silica/alumina ratio. Similarly, when the ratio is determined by thermogravimetric analysis (TGA) of ammonia undergarments, low ammonia titration values may be obtained because the cationic form of aluminum prevents the exchange of ammonium ions to acidic sites. be. These differences are particularly troublesome when using processes such as the dealumination process described below, where the ionic form of aluminum is absent from the zeolite structure. Therefore, care should be taken to measure the framework silica/alumina ratio accurately.

The silica/alumina ratio of a zeolite can be determined by the types of raw materials used in the production of the zeolite and their relative amounts to each other. Therefore, although some variations in the ratio can be obtained by varying the relative concentrations of silica and alumina precursors, certain clear limits can be observed for the maximum silica/alumina ratio that can be achieved for the zeolite. For zeolite beta, this limit is typically 200
7'1 (higher ratios may be obtained) and other operations are usually required to prepare Zeolite I, the desired high siliceous zeolite, with ratios higher than this 200/1.

Dealumination of zeolites can be carried out by contacting the zeolide with an acid, preferably a mineral acid such as hydrochloric acid, and proceeds easily at ambient temperature or under mild heating, and with only a slight loss of crystallinity. However, silica/
High silica forms of zeolite beta with alumina ratios of 200/1 or higher can be readily obtained. Details of this method are described in European Patent Application No. 833027766 (Publication No. 0095304).

It is advantageous to use the hydrogen form of the dealumination zeolite, but other cationic forms can also be used, for example the sodium form. When using these other forms of zeolite, sufficient acid should be used to replace the initial cations in the zeolite with protons. The amount of zeolite in the zeolite/acid mixture should normally be between 5 and 60% by weight.

If desired, the zeolite can be steamed prior to acid extraction to increase the silica/alumina ratio and make the zeolite more stable to acids.

Hydrogenation components/dehydrogenation components are Group Ⅰ and VIA of the periodic table.
One or more metals selected from the group consisting of: The combination of NiO and M o O) is particularly suitable. However, other Groups (I) and (I)A & Genus of the Periodic Table or their oxides or sulfides may also be used. Preferred Group I metals of the Periodic Table include iron, nickel and cobalt, with nickel and cobalt being particularly preferred.

The metals of group I of the periodic table, commonly known as noble metals (e.g. palladium and platinum), are not very effective in desulfurizing and denitrifying the feedstock treated according to the invention; these metals are expensive; It is also more susceptible to poisoning than iron, nickel, and cobalt.

Therefore, base metals from group 1 of the periodic table are suitable as hydrogenation/dehydrogenation components. Because of the greater overall efficiency of base metal-containing catalyst systems, the following statements regarding Group I metal content refer to base metals from Group I of the Periodic Table. When using precious metals, the appropriate range of precious metal content is 0.1 to 5.
m1%.

The content of Group VIA and Group I metals in the catalyst system of the present invention ranges from 0.1 to 10% by weight for Group I metals and from 1 to 20% by weight for Group VIA metals.
The preferred amount of the Group I metal of the Periodic Table is 1 to 5% by weight.0 The preferred amount of the Group VIA metal of the Periodic Table is 5 to 20% by weight. a
1 to 5% by weight of nickel as a compound and 5 to 5% as an oxide
A combination of 20% by weight molybdenum is particularly preferred. The metal amounts mentioned above are based on the weight of the dry catalyst and are expressed in elemental form.

The support for the catalyst system of the present invention preferably contains γ-alumina, but other inorganic oxides include, for example, silica, silica and alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryria, Silica titania, silica alumina doria, silica alumina
It can also contain zirconia, liquor alumina magnesia and silica-magnesia-zirconia. Supports also include those of the montmorillonite and kaolin families, which include subbentonite and kaolin, known as Dexie, Macnamegeorja, and Florida clays, or raw ore components such as Hawaiisite, kaolinite, detsuite, Includes naturally occurring clays such as nacrite or others that are anauxisites. Such clay can be used in its raw, as-mined state, or
R or can be used after acid treatment or chemical modification.

The alumina used is preferably a catalyst that satisfies all of the pore size distribution requirements described above. Especially appropriate! ! The alumina that was detected was American
Cyanamide Company (American Cya)
PA alumina powder manufactured by Na+*id Company. Kaiser 5A
r S A ) and Catapal S B ( Catapal
Other commercially available aluminas such as SB) can be used, but those with some difference in pore size distribution and
It is thought of. However, they can be modified to obtain similar pore size distributions.

Catalysts in which pores less than or equal to 100 Å in diameter represent about 90% of the catalyst pore volume are beneficial. This pore size distribution property is useful for balancing the hydrogenation membrane waxing activity and hydrodesulfurization activity of the catalyst system and for improving the properties and performance of the conventional catalyst.

The zeolite beta content in the support is usually from 0.5 to 30, based on the dry weight of zeolite beta and inorganic oxide.
% by weight, preferably from 1 to 20% by weight.

The alumina content, such as the alumina content, in the support is usually from 99.5 to 70% by weight, based on the dry weight of zeolite beta and hexagonal oxide.

The content of the metals mentioned above as containing metals of group VIA and group I of the periodic table, most preferably di-nogel and molybdenum, ranges from 6 to 25% by weight, expressed in elemental form and based on the total catalyst. be able to.

Metals of group 7 and 'M of the periodic table in the novel catalyst system of the present invention
The relative proportions of Group A metals are not strictly critical; metals from Group VIA of the periodic table, such as molybdenum, are usually available in greater amounts than metals from Group I of the periodic table, such as nickel.

For example, zeolite beta and inorganic oxides may be mixed, then extruded, calcined, ion-exchanged to a low sodium content, dried, impregnated with a Group VIA metal salt solution, dried, and The catalyst can be prepared by impregnation with a Group I metal salt solution and recalcination. Other methods include combining zeolite beta, inorganic oxide support, and hydrogenation/dehydrogenation components, then extruding and calcining, then ion-exchanging the extrudate to a low sodium content, and recalcining. method can be used. Ion exchange is not necessary if the zeolite beta itself has been ion exchanged to a low sodium content before being mixed with alumina and extruded.

The process of the invention can be utilized to upgrade a wide range of petroleum fractions into low pour point middle distillate oils, for example in processes of the type described in U.S. Pat. No. 4,089,775. .

The process of the invention is most effective for treating feedstocks with a sulfur content of at least 1%. Furthermore, the process of the invention can be adapted to treat completely distillable feedstocks and is characterized by a conversion of less than 15% of the feedstock to light substances.

The operating conditions that can be used to carry out the process of the invention can vary depending on the feedstock being treated and the desired specifications for the treated product.Usually the operating conditions utilized are hydrogen pressure. 3.500~21.000kP
a (500-3000 psig), temperature 316-454
C (600-850 below) and a liquid hourly space velocity (LH3V) of 0.1-5 based on the total catalyst loading in the device.

Now, the method of the present invention will be explained with reference to FIGS. 1 to 3.

FIG. 1 is a process diagram for a desulfurization, denitrification and dewaxing process for a charge, which can be any distillable petroleum base oil stock, such as vacuum distilled gas oil, wherein said charge is placed in a conduit (1 ), and hydrogen is introduced via conduit (2) to the reactor (10), and the zero-order heated charge, which is preheated to the desired processing temperature, is transferred via conduit (11) to the reactor (10).
The reactor (20) that sends 15% of the charged raw material to 1
A catalytic hydrogenation clubking zone is provided containing the catalyst of the present invention under conditions effective to convert the material to a boiling point below the initial boiling point of the feedstock in multiple passes. The effluent from reactor (20) containing excess hydrogen contains some free hydrogen sulfide and ammonia because the hydrogenation clubking zone also performs desulfurization, denitrification and dewaxing. Conduit (2
1) to the high pressure gas-liquid separator (30). The hydrogen-rich phase leaves the high pressure gas-liquid separator (30) via conduit (31) and is transferred via conduit (2) to the reactor (20).
Helicycled. The liquid phase is passed through conduit (32) to a low pressure separator (40). Some of the liquid is equilibrated to form a gas phase which is removed from conduit (41).

The remaining liquid phase leaves via conduit (42). The process of FIG. 1 removes relatively large amounts of light materials in the liquid phase from the low pressure separator (40), thereby allowing the production of a low pour point distillate product.

FIG. 2 explains a method for improving the quality of FCC raw materials. This operation involves sending the liquid/phase from the low pressure separator (40) to the rectifier (50) through the conduit (42).
The process is the same as in FIG. 1 except that heavy liquid FCC charge material is produced from 51), naphtha is produced from conduit (52), and distillate is produced from conduit (53). This process produces a low pour point distillate and a hydrotreated FCC charge.

Figure 3 is a process diagram of hydrocracking operation under mild pressure conditions. 1 reactor is a catalytic dewaxing reactor (22)
and a catalytic desulfurization reactor (24).

The feedstock enters the catalytic dewaxing reactor (22) and is catalytically dewaxed under mild pressure conditions with the catalyst of the invention.
The effluent from the hydrodesulphurization reactor (24), which is sent to 4) for further hydrodesulphurization, is sent by conduit (25>) to the high-pressure gas-liquid separator (30) and then by conduit (32). The fuel oil is sent to a low pressure separator (40) and then to a rectification unit (50).The fuel oil is recovered as a residue section by a conduit (54). This is an operation that is performed under certain conditions.

The present invention will be further explained with reference to Examples (hereinafter simply referred to as "examples" unless otherwise specified).

1. 175 g of an extrudate of calcined 15% unsteamed zeolite Beta 85% A ItO3 with a diameter of 1.6 mm (1/16 inch) was impregnated with 127 s1 of ammonium heptamolybdate to the extent that it was barely moist. ℃
(under 250) and then nickel nitrate solution 109m
1 and dry the resulting product, then with a stream of air,
15% unsteamed zeolite beta and 85% A by calcining at 538°C (below 1000°C) for 3 hours
3% NiO and 15% on a support consisting of lzOs.
A catalyst impregnated with MoOs was prepared. The zeolite beta in the fired extrudate is considered to be of type H;
It also had an alpha value of 358.

The alumina was PA alumina powder, a product of American Cyanamid Company.

Fired 100 with a diameter of 1.6ss (1/16 inch)
% alumina cylinder 93.5g ammonium heptamolybdate 71 plow! Impregnate it to the extent that it is barely warm, and
Dry at 21℃ (under 25o) and add nickel nitrate solution 61@
Re-impregnation at 121 °C and 250 °C)
and then dried at 538°C (below 1000°C) in a stream of air for 3
3% on PA alumina support by baking for an hour
A conventional catalyst impregnated with NiO and 15% Mob was prepared.

A comparison of the physical properties of the catalysts obtained in Examples 1 and 2 is given in Table 1 below.

Packing density 0.70 0.74 Particle density 1.20 1.22 True density
3.40 3.95 Pore volume
0.538 0.566 surface area (II
"/IF) 298 242 'Average pore diameter (person) 294 ・" PSD
00~30 people (diameter) 10 1130~
50 11 650~80
44 2980-100 28
43100-150 3 8
150-200 1 1200-30
0 1 0300+
2 21-Σ The catalysts of Examples 1 and 2 were evaluated for the hydrotreatment of vacuum gas oil (V GO) in a batch pressure shaker apparatus. The test conditions used are listed below: VGO, g
150 catalyst, e 20 temperature, °C/below 377/710 pressure (hydrogen),
kP turtle 7000 psig 1000 Reaction time, min 100 The liquid product was atmospherically distilled to obtain a 343°C (below 650) section for analysis. The results are shown in Table 2.

Nitrogen (ppm) 830 350 40
G sulfur (wt%) 2.34 0.415
0.435 pour point ('C/lower) 38/100
21/7O35/95 boiling j■10L logic 1% 2911555 354/670 32
9/62425 396/744 412/
774 395/, 743L-E-' Denitrification rate (%) 58 52 Desulfurization rate (%) 83 82 Pour point reduction ('C) 17 3 (lower) 305 The catalyst of Example 1 containing zeolite beta has excellent denitrification. Nitrogen provided desulfurization and also lowered the pour point by 17°C (below 30°C). In contrast, the g42 conventional catalyst gave good denitrification and desulfurization, but only a lower pour point. The catalysts described above have a similar pore size distribution, i.e. about 90% of the pore volume of each catalyst has a diameter of 10
The pores had a diameter smaller than 0.

[Brief explanation of drawings]

Claims (1)

[Claims] 1. 0.5 to 30% by weight of a distillable petroleum charge having a nitrogen compound, a waxy component and a sulfur content of at least 1.0% by weight and a boiling point of 260°C or higher. a support consisting of zeolite beta of one of said feedstocks in contact with a catalyst containing a hydrogenation/dehydrogenation component which is one Group VIII metal of the Periodic Table and at least one Group VIA metal of the Periodic Table.
A method for simultaneously denitrifying, desulfurizing and dewaxing said feedstock, comprising converting up to 5% to light substances to produce a liquid product with reduced wax content, nitrogen content and sulfur content. 2. Claim 1 in which the inorganic oxide is made of alumina
The method described in section. 3. The catalyst has pores with a diameter of 100 Å or less, which is 9 of the catalyst pore volume.
2. The method according to claim 1 or 2, wherein the method has 0%. 4. Support 1-20% by weight of zeolite beta and 9
4. A method according to any one of claims 1 to 3, containing from 9 to 80% by weight of inorganic oxide. 5. Periodic table V with hydrogenation/dehydrogenation component from 1 to 5% by weight
5. A method according to any one of claims 1 to 4, containing a group III metal and 5 to 20% by weight of a group VIA metal of the periodic table. 6. Nickel is a metal in group VIII of the periodic table, and metal in group V of the periodic table.
6. A method according to any one of claims 1 to 5, wherein the Group IA metal is molybdenum. 7. The method according to claim 6, wherein the nickel is nickel oxide and the molybdenum is molybdenum oxide. 8. Contact in the presence of hydrogen at a total pressure of 3,500 to 21,000
kPa, at a temperature of 316 to 454° C. and a liquid hourly space velocity of 0.1 to 5, based on the total catalyst charge in the apparatus. The method described in.